Chemical intermediates by catalytic fast pyrolysis process

ABSTRACT

In this invention, a portion of the products from a pyrolysis reactor are reacted in a process to form one or more chemical intermediates.

RELATED APPLICATION

This a continuation of application Ser. No. 14/056,723, filed Oct. 17,2013, related to Provisional Application No. 61/715,248, filed Oct. 17,2012, and published as Application Publication No. 2014/0107306 A1 onApr. 17, 2014.

INTRODUCTION

Chemical intermediates are normally derived from fossil resources suchas oil, natural gas, or coal in multi-step processes. In order toreplace or supplement the production of chemical intermediates fromfossil resources, it will be necessary to develop processes thatoriginate from fresh (non-fossil) biological resources, i.e., biomass.The present invention provides methods and systems for making chemicalintermediates from biomass.

Several workers have proposed using biomass-derived products asintermediates for making certain polymers. For example, Kriegel et al.in US 2010/0028512 suggest using biomass-derived ethylene to formpolyethylene. Krieger et al. in US 2009/0246430 and US 2011/0262669describe using biomass-derived ethylene glycol to form PET (polyethyleneterephthalate polymer). Kriegel et al. also suggest usingbiomass-derived terephthalic acid, isophthalic acid, or dimethylterephthalate. Likewise, Cooper et al. in US 2012/0046427 discuss routesfor making polystyrene or PET from biomass-derived intermediates such asethylene, benzene, and p-xylene.

Cortright et al. in WO 2008/109877 discuss the use of oxygenatedhydrocarbons to form a variety of chemical compounds. In some cases, theoxygenates could be derived from pyrolysis. Cortright et al. propose theformation of a myriad of compounds including cyclohexane among thousandsof other compounds.

It is well known that a variety of biomass-derived polymeric materialssuch as lignin, cellulose, and hemi-cellulose, can be pyrolyzed toproduce mixtures of aromatics, olefins, CO, CO2, water, and otherproducts. A particularly desirable form of pyrolysis is known ascatalytic fast pyrolysis (CFP), developed by Professor George Huber, andinvolves the conversion of biomass in a catalytic fluid bed reactor to amixture of aromatics, olefins, CO, CO2, char, ash, and a variety ofother organics. The aromatics include benzene, toluene, xylenes, andnaphthalene (BTXN), among other aromatics. The olefins include ethylene(30-60% of olefins), propylene (30-50%), and lesser amounts of higherolefins. BTXN have high value and are easily transported.

It is an object of this invention to provide methods for the productionof chemical intermediates from the primary products of CFP (i.e.,aromatics, olefins, CO) that can be integrated with CFP in advantageousways that improve the overall yield of intermediates, improve thethermal balance, generate useful and different by-products, and/orgenerate integrated processes for the production of chemicals fromrenewable resources. For example, it is an object of this invention toprovide integrated processes for the production of ethylene oxide,ethanol, acetic acid, acetaldehyde, styrene, cumene, terephthalic acid,phthalic anhydride, phenol. ethylbenzene, cyclohexane, adipic acid,benzaldehyde, toluene diisocyanate, toluene diamine, methylene diphenyldiisocyanate, polyurethanes, polycarbonates, and other chemicalintermediates by the conversion of benzene, toluene, xylenes,naphthalene, ethylene, propylene, and butylenes prepared by catalyticfast pyrolysis.

SUMMARY OF THE INVENTION

Generally, the invention includes any of the methods, apparatus andsystems that are described herein; particularly involving pyrolysis ofbiomass and conversion of at least one pyrolysis product to anotherchemical compound.

In one aspect, the invention provides a method for producing one or morefluid hydrocarbon products from a hydrocarbonaceous material comprisingfeeding a hydrocarbonaceous material to a reactor, and pyrolyzing withinthe reactor at least a portion of the hydrocarbonaceous material underreaction conditions sufficient to produce one or more pyrolysisproducts, catalytically reacting at least a portion of the pyrolysisproducts, separating at least a portion of the hydrocarbon products, andreacting a portion of said hydrocarbon products to produce a chemicalintermediate. Preferably, all of these steps are conducted within anintegrated reactor system. An integrated reactor system is defined ascomprising both apparatus and chemical composition(s) within theapparatus.

In the present invention, a preferred apparatus comprises a biomassconveyor, a catalyst-containing pyrolysis reactor, a primary productseparator, a primary product upgrader, and a secondary productseparator. At least a portion of the primary products comprise aromaticsand/or olefins. The secondary products, also called chemicalintermediates, comprise ethylene oxide, ethanol, acetic acid,acetaldehyde, acrylonitrile, acrylic acid, styrene, cumene,ethylbenzene, terephthalic acid, dimethyl terephthalate,polyethyleneterephthalate (PET), polybutylene terephthalate, phthalicanhydride, phenol, ethylbenzene, cyclohexane, adipic acid, benzaldehyde,benzoic acid, hexanes, ethylene glycol, polyethylene,hexamethylenediamine, adiponitrile, Nylon 6, Nylon 6,6, toluenediisocyanate, toluene diamine, methylene diphenyl diisocyanate,polyurethanes, polycarbonates, alkylphenols, polymethylphenols,ethylphenols, isopropylphenols, sec-butylphenols, tert-butylphenols,tert-pentylphenols, cycloalkylphenols, aralkylphenols, alkenylphenols,indanols, catechol, trihydroxybenzenes, pyrogallol, hydroxyhydroquinone,phloroglucinol, bisphenols (bishydroxyarylalkanes), hydroxybiphenyls,phenol ethers and mixtures thereof. In some embodiments, at least aportion of: the primary products, and/or partially deactivated catalystfrom a catalytic fast pyrolysis reactor, and/or secondary products, orsome combination of these, are oxidized to provide heat for the biomassupgrading process. In some embodiments the chemical intermediateproducts are processed by processes such as blow-molding, extrusion,stamping, pressing or otherwise to form bottles, sheets, fibers, plates,or other useful shapes.

The invention can be further characterized by one or more (that is, anycombination) of the following features: at least a portion of thebyproducts of the chemical intermediate production are returned to thepyrolysis reactor; at least a portion of one benzene-rich fractionseparated from the hydrocarbon products is alkylated with an olefin toproduce a chemical intermediate (in some preferred embodiments, anolefin produced from the catalytic fast pyrolysis process is used atleast in part for the alkylation; in some preferred embodiments theolefin comprises ethylene and/or propylene); at least a portion of onebenzene-rich fraction separate from the hydrocarbon products is oxidizedto produce phenol; at least a portion of one benzene-rich fractionseparated from the hydrocarbon products is hydrogenated to producecyclohexane, and in some embodiments at least a portion of thecyclohexane is oxidized to adipic acid (in some embodiments, the adipicacid is polymerized in the same integrated system); at least a portionof one toluene-rich fraction separated from the hydrocarbon products issubjected to a disproportionation reaction to produce a xylenes-enrichedproduct stream; at least a portion of one toluene-rich fractionseparated from the hydrocarbon products is subjected to a methylationreaction to produce a xylenes-enriched product stream; at least aportion of one para-xylene-rich fraction separated from, or otherwisederived from the hydrocarbon products is oxidized to produceterephthalic acid that, optionally is polymerized to poly(ethyleneterephthalate) (PET), poly(butylene terephthalate) (PBT), orpoly(trimethylene terephthalate) (PTT); at least a portion of oneortho-xylene rich fraction separated from the hydrocarbon products isoxidized to produce phthalic anhydride (in some embodiments, at least aportion of the phthalic anhydride is esterified to produce a phthalatediester); at least a portion of one ethylbenzene-rich fraction separatedfrom, or otherwise derived from the hydrocarbon products isdehydrogenated to produce styrene that, optionally, is polymerized topolystyrene; the fluid hydrocarbon products comprise olefins (preferablycombined with a step of polymerizing the olefins or reacting the olefinswith aromatics); the fluid hydrocarbon products comprise aromatics(which may be alkylated) and the aromatics are subjected to one or moreof the following: dehydrogenation (optionally followed bypolymerization), hydrogenated to paraffins, or oxidized to acids,anhydrides, aldehydes, alcohols or epoxides (the epoxides may besubsequently polymerized).

The invention also provides a method for producing one or more fluidhydrocarbon products from a hydrocarbonaceous material comprising:feeding a hydrocarbonaceous material to a reactor; pyrolyzing within thereactor at least a portion of the hydrocarbonaceous material underreaction conditions sufficient to produce one or more pyrolysisproducts; catalytically reacting within the reactor at least a portionof the one or more pyrolysis products under reaction conditionssufficient to produce one or more fluid hydrocarbon products comprisingolefins and aromatics; reacting at least a portion of said fluidhydrocarbon products to produce at least one chemical intermediate; andfeeding at least a portion of the byproducts of the chemicalintermediate production back to the pyrolysis reactor.

In some embodiments, the methods use a recycle step in which therecycled compounds do not consist primarily of olefins, nor of compoundsproduced during catalyst regeneration.

The invention also provides for a method of oxidizing p-xylene usingpyrolysis products other than acetic acid.

Another concept is for a method of sequestering carbon comprisingconverting biomass to polystyrene, forming cups from the polystyrene,and burying or recycling the cups. In some preferred embodiments, thepolystyrene is formed in the same facility in which biomass ispyrolyzed. In this fashion, consumers can use disposable polystyrenecups while being assured that the cups do not contribute to increasedcarbon in the atmosphere. As in any of the inventive methods, thepresence of biomass-derived materials can be confirmed by measuring thepresence of ¹⁴C in the material.

The invention includes methods, apparatus, and systems (which compriseapparatus plus process streams (that is, fluid compositions) and mayfurther be characterized by conditions such as temperature or pressure).Thus, any of the descriptions herein apply to the inventive methods,apparatus and systems.

The hydrocarbonaceous material that is fed to the reactor typicallycomprises a solid hydrocarbonaceous material, often in the presence of agas phase. In some preferred embodiments, the hydrocarbonaceous materialis at least 90 mass % solids. In some lesser preferred embodiments thehydrocarbonaceous material could be only in the gas and/or a liquid orslurry phase. In some embodiments, a recycle stream, preferably anaqueous recycle stream can be contacted with the hydrocarbonaceousmaterial before the hydrocarbonaceous material is fed to the reactor.

In preferred embodiments of the inventive method, apparatus, and/orsystem, the pyrolysis reactor contains a solid catalyst. The solidcatalyst preferably comprises a zeolite, more preferably a zeolite and ametal and/or a metal oxide. The solid catalyst in the CFP reactor maycomprise elements such as, for example, silicon, aluminum, titanium,vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc,gallium, platinum, palladium, silver, tin, phosphorus, sodium,potassium, magnesium, calcium, tungsten, zirconium, cerium, lanthanum,and combinations thereof. Additional catalyst materials or inert solidsmay also be present. In some preferred embodiments, the CFP reaction iscatalyzed by a zeolite. In some embodiments, the zeolite comprises poresizes in the range of 5.0 to 6.5 angstroms. In some preferredembodiments, the catalyst comprises ZSM-5. In some preferredembodiments, the mass ratio of catalyst fed to the reactor tohydrocarbonaceous material fed to the reactor is between 0.1 and 20.

In some embodiments, an aqueous phase is recovered from the CFP reactorand carbonaceous material is removed from the aqueous phase and at leasta portion of the separated carbonaceous materials is recycled to the CFPreactor. Preferably, the separated carbonaceous phase comprises olefins,aromatics, or oxygenates, or a mixture of these, and at least a portionof these are fed to the CFP reactor. This can be done, for example, by astripping process in which a liquid phase is contacted with a gas (suchas by bubbling a gas through the liquid) and the resulting gas phase,which is enriched with at least one component from the liquid phase, ispassed into the reactor. Alternatively, the liquid phase can be strippedand then the liquid phase, now at least partly depleted of at least onecomponent, is recycled to the reactor. As with any of the recycle steps,the return flow may be directly into the reactor or at any stage in aflow path prior to the reactor stage.

In preferred embodiments, the CFP reactor is a fluidized bed,circulating bed, or riser reactor. In some preferred embodiments, thetemperature within the reactor is between 300 and 1000° C.

The hydrocarbonaceous material fed to the reactor may comprise a biomassmaterial; or plastic waste, recycled plastics, agricultural andmunicipal solid waste, food waste, animal waste, carbohydrates, orlignocellulosic materials; or the hydrocarbonaceous material cancomprise xylitol, glucose, cellobiose, cellulose, hemi-cellulose, orlignin; or the hydrocarbonaceous material may comprise sugar canebagasse, glucose, wood, or corn stover, or any of these materials in anycombination.

In any of the inventive aspects, the pyrolysis step(s), (and/or anyselected process step) may preferably be conducted at a pressure(absolute) of 30 atm or less, more preferably of less than 10 atm, insome embodiments less than 1 atm; and in some embodiments in the rangeof 0.1 to 10 atm.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the catalytic fast pyrolysis process.

FIG. 2 illustrates processes for converting biomass to chemicalintermediates incorporating catalytic fast pyrolysis.

DETAILED DESCRIPTION OF THE INVENTION Glossary Aromatics

As used herein, the terms “aromatics” or “aromatic compound” refer to ahydrocarbon compound or compounds comprising one or more aromatic groupssuch as, for example, single aromatic ring systems (e.g., benzyl,phenyl, etc.) and fused polycyclic aromatic ring systems (e.g. naphthyl,1,2,3,4-tetrahydronaphthyl, etc.). Examples of aromatic compoundsinclude, but are not limited to, benzene, toluene, indane, indene,2-ethyl toluene, 3-ethyl toluene, 4-ethyl toluene, trimethylbenzene(e.g., 1,3,5-trimethyl benzene, 1,2,4-trimethyl benzene, 1,2,3-trimethylbenzene, etc.), ethylbenzene, styrene, cumene, methylbenzene,propylbenzene, xylenes (e.g., p-xylene, m-xylene, o-xylene, etc.),naphthalene, methyl-naphthalene (e.g., 1-methyl naphthalene, anthracene,9.10-dimethylanthracene, pyrene, phenanthrene, dimethyl-naphthalene(e.g., 1,5-dimethylnaphthalene, 1,6-dimethylnaphthalene,2,5-dimethylnaphthalene, etc.), ethyl-naphthalene, hydrindene,methyl-hydrindene, and dimethyl-hydrindene. Single-ring and/or higherring aromatics may also be produced in some embodiments. Aromatics alsoinclude single and multiple ring compounds that contain heteroatomsubstituents, i.e. phenol, cresol, benzofuran, etc.

Biomass

As used herein, the term “biomass” is given its conventional meaning inthe art and refers to any organic source of energy or chemicals that isrenewable. Its major components can be: (1) trees (wood) and all othervegetation; (2) agricultural products and wastes (corn, fruit, garbageensilage, etc.); (3) algae and other marine plants; (4) metabolic wastes(manure, sewage), and (5) cellulosic urban waste. Examples of biomassmaterials are described, for example, in Huber, G. W. et al, “Synthesisof Transportation Fuels from Biomass: Chemistry, Catalysts, andEngineering,” Chem. Rev. 106, (2006), pp. 4044-4098.

Biomass is conventionally defined as the living and recently deadbiological material that can be converted for use as fuel or forindustrial production. The criterion as biomass is that the materialshould be recently participating in the carbon cycle so that the releaseof carbon in the combustion process results in no net increase averagedover a reasonably short period of time (for this reason, fossil fuelssuch as peat, lignite and coal are not considered biomass by thisdefinition as they contain carbon that has not participated in thecarbon cycle for a long time so that their combustion results in a netincrease in atmospheric carbon dioxide). Most commonly, biomass refersto plant matter grown for use as biofuel, but it also includes plant oranimal matter used for production of fibers, chemicals or heat. Biomassmay also include biodegradable wastes or byproducts that can be burnt asfuel or converted to chemicals, including municipal wastes, green waste(the biodegradable waste comprised of garden or park waste, such asgrass or flower cuttings and hedge trimmings), byproducts of farmingincluding animal manures, food processing wastes, sewage sludge, blackliquor from wood pulp or algae. Biomass excludes organic material whichhas been transformed by geological processes into substances such ascoal, oil shale or petroleum. Biomass is widely and typically grown fromplants, including miscanthus, spurge, sunflower, switchgrass, hemp, corn(maize), poplar, willow, sugarcane, and oil palm (palm oil) with theroots, stems, leaves, seed husks and fruits all being potentiallyuseful. The particular plant or other biomass source used is notimportant to the product chemical or fuel although the processing of theraw material for introduction to the processing unit will vary accordingto the needs of the unit and the form of the biomass.

Biomass-Derived

Any of the products, processes, and/or systems described herein may beadditionally characterized by the fact that they are biomass-derived,meaning that the products are at least partly derived from biomass, and,in most cases are 100% derived from biomass. As is well-known, thepresence of biomass-derived material can be readily ascertained by thepresence of ¹⁴C, which is essentially not present in fossil fuels.

Biomass Feed Particle Sizes

The hydrocarbonaceous material in the feed composition may comprise asolid, liquid, and/or gas. In cases where the hydrocarbonaceous materialincludes solids, the solids may be of any suitable size. In some cases,it may be advantageous to use hydrocarbonaceous solids with relativelysmall particle sizes. Small-particle solids may, in some instances,react more quickly than larger solids due to their relatively highersurface area-to-volume ratios compared to larger solids. In addition,small particle sizes may allow for more efficient heat transfer withineach particle and/or within the reactor volume. This may prevent orreduce the formation of undesired reaction products. Moreover, smallparticle sizes may provide for increased solid-gas and solid-solidcontact, leading to improved heat and mass transfer.

Biomass Pyrolysis Liquid

Biomass pyrolysis liquid or bio-oil is the liquid fraction that can beisolated from a pyrolysis reaction of biomass. Biomass pyrolysis liquidis usually dark brown and approximates to biomass in elementalcomposition. It is composed of a very complex mixture of oxygenatedhydrocarbons with an appreciable proportion of water from both theoriginal moisture and reaction product. Compositionally, the biomasspyrolysis oil will vary with the type of biomass, but is known toconsist of oxygenated low molecular weight alcohols (e.g., furfurylalcohol), aldehydes (aromatic aldehydes), ketones (furanone), phenols(methoxy phenols) and water. Solid char may also be present, suspendedin the oil. The liquid is formed by rapidly quenching the intermediateproducts of flash pyrolysis of hemicellulose, cellulose, and lignin inthe biomass. Chemically, the oil contains several hundred differentchemicals in widely varying proportions, ranging from formaldehyde andacetic acid to complex, high molecular weight phenols, anhydrosugars andother oligosaccharides. It has a distinctive odor from low molecularweight aldehydes and acids, is usually acidic with a pH of 1.5-3.8, andcan be an irritant.

Catalysts

Catalyst components useful in the context of this invention can beselected from any catalyst known in the art, or as would be understoodby those skilled in the art. Catalysts promote and/or effect reactions.Thus, as used herein, catalysts lower the activation energy (increasethe rate) of a chemical process, and/or improve the distribution ofproducts or intermediates in a chemical reaction (for example, a shapeselective catalyst). Examples of reactions that can be catalyzedinclude: dehydration, dehydrogenation, isomerization, hydrogen transfer,aromatization, decarbonylation, decarboxylation, aldol condensation, andcombinations thereof. Catalyst components can be considered acidic,neutral or basic, as would be understood by those skilled in the art.

For fast catalytic pyrolysis, particularly advantageous catalystsinclude those containing internal porosity selected according to poresize (e.g., mesoporous and pore sizes typically associated withzeolites), e.g., average pore sizes of less than about 100 Angstroms,less than about 50 Angstroms, less than about 20 Angstroms, less thanabout 10 Angstroms, less than about 5 Angstroms, or smaller. In someembodiments, catalysts with average pore sizes of from about 5 Angstromsto about 100 Angstroms may be used. In some embodiments, catalysts withaverage pore sizes of between about 5.5 Angstroms and about 6.5Angstroms, or between about 5.9 Angstroms and about 6.3 Angstroms may beused. In some cases, catalysts with average pore sizes of between about7 Angstroms and about 8 Angstroms, or between about 7.2 Angstroms andabout 7.8 Angstroms may be used.

In some preferred embodiments of CFP, the catalyst may be selected fromnaturally occurring zeolites, synthetic zeolites and combinationsthereof. In certain embodiments, the catalyst may be a ZSM-5 zeolitecatalyst, as would be understood by those skilled in the art.Optionally, such a catalyst can comprise acidic sites. Other types ofzeolite catalysts include: ferrierite, zeolite Y, zeolite beta,mordenite, MCM-22, ZSM-23, ZSM-57, SUZ-4, EU-1, ZSM-11, (S)A1P0-31,SSZ-23, among others. In other embodiments, non-zeolite catalysts may beused; for example, WO_(x)/ZrO₂, aluminum phosphates, etc. In someembodiments, the catalyst may comprise a metal and/or a metal oxide.Suitable metals and/or oxides include, for example, nickel, palladium,platinum, titanium, vanadium, chromium, manganese, iron, cobalt, zinc,copper, gallium, and/or any of their oxides, among others. In some casespromoter elements chosen from among the rare earth elements, i.e.,elements 57-71, cerium, zirconium or their oxides for combinations ofthese may be included to modify activity or structure of the catalyst.In addition, in some cases, properties of the catalysts (e.g., porestructure, type and/or number of acid sites, etc.) may be chosen toselectively produce a desired product.

Catalysts for other processes, such as alkylation of olefins arewell-known and can be selected for the treatment processes describedherein.

Catalyst Residence Time

The catalyst residence time of the catalyst in the reactor is defined asthe volume of the reactor filled with catalyst divided by the volumetricflow rate of the catalyst through the reactor. For example, if a 3-literreactor contains 2 liters of catalyst and a flow of 0.4 liters perminute of catalyst is fed through the reactor, i.e., both fed andremoved, the catalyst residence time is 2/0.4 minutes, or 5 minutes.

Contact Time

Contact time is the residence time of a material in a reactor or otherdevice, when measured or calculated under standard conditions oftemperature and pressure, i.e., 0° C. and 1 atm. For example, a 2-literreactor to which is fed 3 standard liters per minute of gas has acontact time of 2/3 minute, or 40 seconds for that gas. For a chemicalreaction, contact time or residence time is based on the volume of thereactor, where substantial reaction is occurring, and would excludevolume where substantially no reaction is occurring, such as an inlet oran exhaust conduit. For catalyzed reactions, the volume of a reactionchamber is the volume where catalyst is present.

Conversion

The term “conversion of a reactant” refers to the reactant mole or masschange between a material flowing into a reactor and a material flowingout of the reactor divided by the moles or mass of reactant in thematerial flowing into the reactor. For example, if 100 grams of ethyleneare fed to a reactor and 30 grams of ethylene are flowing out of thereactor, the conversion is [(100−30)/100]=70% conversion of ethylene.

Fluid

The term “fluid” refers to a gas, a liquid, a mixture of a gas and aliquid, or a gas or a liquid containing dispersed solids, liquiddroplets and/or gaseous bubbles. The terms “gas” and “vapor” have thesame meaning and are sometimes used interchangeably. In someembodiments, it may be advantageous to control the residence time of thefluidization fluid in the reactor. The fluidization residence time ofthe fluidization fluid is defined as the volume of the reactor dividedby the volumetric flow rate of the fluidization fluid under processconditions of temperature and pressure.

Fluidized Bed Reactor

As used herein, the term “fluidized bed reactor” is given itsconventional meaning in the art and is used to refer to reactorscomprising a vessel that can contain a granular solid material (e.g.,silica particles, catalyst particles, etc.), in which a fluid (e.g., agas or a liquid) is passed through the granular solid material atvelocities sufficiently high as to suspend the solid material and causeit to behave as though it were a fluid. The term “circulating fluidizedbed reactor” is also given its conventional meaning in the art and isused to refer to fluidized bed reactors in which the granular solidmaterial is passed out of the reactor, circulated through a line influid communication with the reactor, and recycled back into thereactor.

Bubbling fluidized bed reactors and turbulent fluidized bed reactors arealso known to those skilled in the art. In bubbling fluidized bedreactors, the fluid stream used to fluidize the granular solid materialis operated at a sufficiently low flow rate such that bubbles and voidsare observed within the volume of the fluidized bed during operation. Inturbulent fluidized bed reactors, the flow rate of the fluidizing streamis higher than that employed in a bubbling fluidized bed reactor, andhence, bubbles and voids are not observed within the volume of thefluidized bed during operation.

Examples of fluidized bed reactors, circulating fluidized bed reactors,bubbling and turbulent fluidized bed reactors are described inKirk-Othmer Encyclopedia of Chemical Technology (online), Vol. 11,Hoboken, N.J.: Wiley-Interscience, c2001-, pages 791-825, and in“Fluidization Engineering”, 2″d Edition, by D. Kunii and O. Levenspiel,Butterworth-Heinemann, 1991, Newton, Mass., both of which areincorporated herein by reference.

Olefins

As used herein, the terms “olefin” or “olefin compound” (a.k.a.“alkenes”) are given their ordinary meaning in the art, and are used torefer to any unsaturated hydrocarbon containing one or more pairs ofcarbon atoms linked by a double bond. Olefins include both cyclic andacyclic (aliphatic) olefins, in which the double bond is located betweencarbon atoms forming part of a cyclic (closed-ring) or of an open-chaingrouping, respectively. In addition, olefins may include any suitablenumber of double bonds (e.g., mono olefins, diolefins, triolefins,etc.). Examples of olefin compounds include, but are not limited to,ethene, propene, allene (propadiene), 1-butene, 2-butene, isobutene (2methyl propene), butadiene, and isoprene, among others. Examples ofcyclic olefins include cyclopentene, cyclohexane, and cycloheptene,among others. Aromatic compounds such as toluene are not consideredolefins; however, olefins that include aromatic moieties are consideredolefins, for example, benzyl acrylate or styrene.

Pore Size

Pore size relates to the size of a molecule or atom that can penetrateinto the pores of a material. As used herein, the term “pore size” forzeolites and similar catalyst compositions refers to the Norman radiiadjusted pore size well known to those skilled in the art. Determinationof Norman radii adjusted pore size is described, for example, in Cook,M.; Conner, W. C., “How big are the pores of zeolites?” Proceedings ofthe International Zeolite Conference, 12th, Baltimore, Jul. 5-10, 1998;(1999), 1, pp 409-414, which is incorporated herein by reference in itsentirety. As a specific exemplary calculation, the atomic radii forZSM-5 pores are about 5.5-5.6 Angstroms, as measured by x-raydiffraction. In order to adjust for the repulsive effects between theoxygen atoms in the catalyst, Cook and Conner have shown that the Normanadjusted radii are 0.7 Angstroms larger than the atomic radii (about6.2-6.3 Angstroms).

One of ordinary skill in the art will understand how to determine thepore size (e g, minimum pore size, average of minimum pore sizes) in acatalyst. For example, x-ray diffraction (XRD) can be used to determineatomic coordinates. XRD techniques for the determination of pore sizeare described, for example, in Pecharsky, V. K. et al, “Fundamentals ofPowder Diffraction and Structural Characterization of Materials,”Springer Science+Business Media, Inc., New York, 2005, incorporatedherein by reference in its entirety. Other techniques that may be usefulin determining pore sizes (e.g., zeolite pore sizes) include, forexample, helium pycnometry or low-pressure argon adsorption techniques.These and other techniques are described in Magee, J. S. et al, “FluidCatalytic Cracking: Science and Technology,” Elsevier PublishingCompany, Jul. 1, 1993, pp. 185-195, which is incorporated herein byreference in its entirety. Pore sizes of mesoporous catalysts may bedetermined using, for example, nitrogen adsorption techniques, asdescribed in Gregg, S. J. at al, “Adsorption, Surface Area, andPorosity,” 2nd Ed., Academic Press Inc., New York, 1982 and Rouquerol,F. et al, “Adsorption by powders and porous materials. Principles,Methodology, and Applications,” Academic Press Inc., New York, 1998,both incorporated herein by reference in their entirety.

In some embodiments, a screening method is used to select catalysts withappropriate pore sizes for the conversion of specific pyrolysis productmolecules. The screening method may comprise determining the size ofpyrolysis product molecules desired to be catalytically reacted (e.g.,the molecule kinetic diameters of the pyrolysis product molecules). Oneof ordinary skill in the art can calculate, for example, the kineticdiameter of a given molecule. The type of catalyst may then be chosensuch that the pores of the catalyst (e.g., Norman adjusted minimumradii) are sufficiently large to allow the pyrolysis product moleculesto diffuse into and/or react with the catalyst. In some embodiments, thecatalysts are chosen such that their pore sizes are sufficiently smallto prevent entry and/or reaction of pyrolysis products whose reactionwould be undesirable.

Pyrolysis

As used herein, the terms “pyrolysis” and “pyrolyzing” are given theirconventional meaning in the art and are used to refer to thetransformation of a compound, e.g., a solid hydrocarbonaceous material,into one or more other substances, e.g., volatile organic compounds,gases, and coke, by heat, preferably without the addition of, or in theabsence of, O₂. Preferably, the volume fraction of O₂ present in apyrolysis reaction chamber is 0.5% or less. Pyrolysis may take placewith or without the use of a catalyst. “Catalytic pyrolysis” refers topyrolysis performed in the presence of a catalyst, and may involve stepsas described in more detail below. Example of catalytic pyrolysisprocesses are outlined, for example, in Huber, G. W. et al, “Synthesisof Transportation Fuels from Biomass: Chemistry, Catalysts, andEngineering,” Chem. Rev. 106, (2006), pp. 4044-4098.

Residence Time

Residence time is defined as the volume of the reactor or device, orspecific portion of a device, divided by the exit flow of all gases outof the reactor, or device or portion of the reactor or device, includingfluidization gas, products, and impurities, measured or calculated atthe average temperature of the reactor or device and the exit pressureof the reactor or device or portion thereof.

Selectivity

The term “selectivity” refers to the amount of production of aparticular product in comparison to a selection of products. Selectivityto a product may be calculated by dividing the amount of the particularproduct by the amount of a number of products produced. For example, if75 grams of aromatics are produced in a reaction and 20 grams of benzeneare found in these aromatics, the selectivity to benzene amongstaromatic products is 20/75=26.7%. Selectivity can be calculated on amass basis, as in the aforementioned example, or it can be calculated ona carbon basis, where the selectivity is calculated by dividing theamount of carbon that is found in a particular product by the amount ofcarbon that is found in a selection of products. Unless specifiedotherwise, for reactions involving biomass as a reactant, selectivity ison a mass basis. For reactions involving conversion of a specificmolecular reactant (ethene, for example), selectivity is the percentage(on a mass basis unless specified otherwise) of a selected productdivided by all the products produced.

Yield

The term yield is used herein to refer to the amount of a productflowing out of a reactor divided by the amount of reactant flowing intothe reactor, usually expressed as a percentage or fraction. Yields areoften calculated on a mass basis, carbon basis, or on the basis of aparticular feed component. Mass yield is the mass of a particularproduct divided by the weight of feed used to prepare that product. Forexample, if 500 grams of biomass is fed to a reactor and 45 grams ofbenzene is produced, the mass yield of benzene would be 45/500=9%benzene. Carbon yield is the mass of carbon found in a particularproduct divided by the mass of carbon in the feed to the reactor. Forexample, if 500 grams of biomass that contains 40% carbon is reacted toproduce 45 grams of benzene that contains 92.3% carbon, the carbon yieldis [(45*0.923)/(500*0.40)]=20.8%. Carbon yield from biomass is the massof carbon found in a particular product divided by the mass of carbonfed to the reactor in a particular feed component. For example, if 500grams of biomass containing 40% carbon and 100 grams of CO2 are reactedto produce 40 g of benzene (containing 92.3% carbon), the carbon yieldon biomass is [(40*0.923)/(500*0.40)]=18.5%; note that the mass of CO₂does not enter into the calculation.

As is standard patent terminology, the term “comprising” means“including” and does not exclude additional components. Any of theinventive aspects described in conjunction with the term “comprising”also include narrower embodiments in which the term “comprising” isreplaced by the narrower terms “consisting essentially of” or“consisting of.” As used in this specification, the terms “includes” or“including” should not be read as limiting the invention but, rather,listing exemplary components.

In some embodiments, the feed composition (e.g., in feed stream 6 ofFIG. 1) comprises a mixture of hydrocarbonaceous material and acatalyst. The mixture may comprise, for example, solids, liquids, and/orgases. In certain embodiments, the mixture comprises a composition of asolid catalyst and a solid hydrocarbonaceous material. In otherembodiments, a catalyst may be provided separately from the reactor feedstream. In some embodiments the feed may be kept in an inert atmosphereor an atmosphere formed by the vent gases from the process, 74.

In some embodiments, for example when solid hydrocarbonaceous materialsare used, moisture may optionally be removed from the feed compositionprior to being fed to the reactor, e.g., by an optional dryer 10.Removal of moisture from the feed stream may be advantageous for severalreasons. For example, the moisture in the feed stream may requireadditional energy input in order to heat the feed to a temperaturesufficiently high to achieve pyrolysis. Variations in the moisturecontent of the feed may lead to difficulties in controlling thetemperature of the reactor. In addition, removal of moisture from thefeed can reduce or eliminate the need to process the water during laterprocessing steps.

In some embodiments, the feed composition may be dried until the feedcomposition comprises less than 10%, less than 5%, less than 2%, or lessthan 1% water by weight. Suitable equipment capable of removing waterfrom the feed composition is known to those skilled in the art. As anexample, in one set of embodiments, the dryer comprises an oven heatedto a particular temperature (e.g., at least 80° C., at least 100° C., atleast 150° C., or higher) through which the feed composition iscontinuously, semi-continuously, or periodically passed. In some cases,the dryer may comprise a vacuum chamber into which the feed compositionis processed as a batch. Other embodiments of the dryer may combineelevated temperatures with vacuum operation. The dryer may be integrallyconnected to the reactor or may be provided as a separate unit from thereactor.

In some instances, the particle size of the feed composition may bereduced in an optional grinding system 12 prior to passing the feed tothe reactor. In some embodiments, the average diameter of the groundfeed composition exiting the grinding system may comprise no more thanabout 50%, not more than about 25%, no more than about 10%, no more thanabout 5%, no more than about 2% of the average diameter of the feedcomposition fed to the grinding system. Large-particle feed material maybe more easily transportable and less difficult to process thansmall-particle feed material. On the other hand, in some cases it may beadvantageous to feed small particles to the reactor (as discussedbelow). The use of a grinding system allows for the transport oflarge-particle feed between the source and the process, while enablingthe feed of small particles to the reactor.

Suitable equipment capable of grinding the feed composition is known tothose skilled in the art. For example, the grinding system may comprisean industrial mill (e.g., hammer mill, ball mill, etc.), a unit withblades (e.g., chipper, shredder, etc.), or any other suitable type ofgrinding system. In some embodiments, the grinding system may comprise acooling system (e.g., an active cooling systems such as a pumped fluidheat exchanger, a passive cooling system such as one including fins,etc.), which may be used to maintain the feed composition at relativelylow temperatures (e.g., ambient temperature) prior to introducing thefeed composition to the reactor. The grinding system may be integrallyconnected to the reactor or may be provided as a separate unit from thereactor. While the grinding step is shown following the drying step inFIG. 1, the order of these operations may be reversed in someembodiments. In still other embodiments, the drying and grinding stepsmay be achieved using an integrated unit.

In some cases, grinding and cooling of the hydrocarbonaceous materialmay be achieved using separate units. Cooling of the hydrocarbonaceousmaterial may be desirable, for example, to reduce or prevent unwanteddecomposition of the feed material prior to passing it to the reactor.In one set of embodiments, the hydrocarbonaceous material may be passedto a grinding system to produce a ground hydrocarbonaceous material. Theground hydrocarbonaceous material may then be passed from the grindingsystem to a cooling system and cooled. The hydrocarbonaceous materialmay be cooled to a temperature of lower than about 300° C., lower thanabout 200° C., lower than about 100° C., lower than about 75° C., lowerthan about 50° C., lower than about 35° C., or lower than about 20° C.prior to introducing the hydrocarbonaceous material into the reactor. Inembodiments that include the use of a cooling system, the cooling systemincludes an active cooling unit (e.g., a heat exchanger) capable oflowering the temperature of the biomass. In some embodiments, two ormore of the drier, grinding system, and cooling system unit operationsmay be combined into a single unit. The cooling system may be, in someembodiments, directly integrated with one or more reactors.

As illustrated in FIG. 1, the feed composition may be transferred toreactor 20. The feed may be kept under an inert atmosphere such as thevent gas 74 or other suitable gas. Fluids such as recycle gas 102, ventgas 74 or other fluids may be fed along with the solid hydrocarbonaceousfeed into reactor 20 in order to facilitate smooth feed flow. Optionallya portion of the aqueous phase 84 or organic phase 94 may be fed alongwith the hydrocarbonaceous feed. Aqueous phase 84 or organic phase 94may optionally be combined to be fed to reactor 20 or may be fedseparately.

The reactor may be used, in some instances, to perform catalyticpyrolysis of hydrocarbonaceous material. In the illustrative embodimentof FIG. 1, the reactor comprises any suitable reactor known to thoseskilled in the art. For example, in some instances, the reactor maycomprise a continuously stirred tank reactor (CSTR), a batch reactor, asemi-batch reactor, or a fixed bed catalytic reactor, among others. Insome cases, the reactor comprises a fluidized bed reactor, e.g., acirculating fluidized bed reactor, a moving bed reactor such as a riserreactor, or a bubbling bed reactor or turbulent bed reactor. Fluidizedbed reactors may, in some cases, provide improved mixing of the catalystand/or hydrocarbonaceous material during pyrolysis and/or subsequentreactions, which may lead to enhanced control over the reaction productsformed. The use of fluidized bed reactors may also lead to improved heattransfer within the reactor. In addition, improved mixing in a fluidizedbed reactor may lead to a reduction of the amount of coke adhered to thecatalyst, resulting in reduced deactivation of the catalyst in somecases. Throughout this specification, various compositions are referredto as process streams; however, it should be understood that theprocesses could also be conducted in batch mode.

In the set of embodiments illustrated in FIG. 1, separated catalyst mayexit the solids separator via stream 42. In some cases, the catalystexiting the separator may be at least partially deactivated. Theseparated catalyst 42 may be fed, in some embodiments, to a regenerator30 in which any catalyst that was at least partially deactivated may bere-activated. Used catalyst also exits reactor 20 via stream 22 so thata flow of catalyst through the reactor is established. The separatedcatalyst 42 may be combined with used catalyst stream 22 before feedingto regenerator 30. In some embodiments, the regenerator may compriseoptional purge stream 38, which may be used to purge coke, ash, and/orcatalyst from the regenerator. Methods for activating and regeneratingcatalyst are well-known to those skilled in the art, for example, asdescribed in Kirk-Othmer Encyclopedia of Chemical Technology (Online),Vol. 5, Hoboken, N.J.: Wiley-Interscience, 2001, pages 255-322.

In one set of embodiments, an oxidizing agent is fed to the regeneratorvia a stream 32, e.g., as shown in FIG. 1. The oxidizing agent mayoriginate from any source including, for example, a tank of oxygen,atmospheric air, or steam, among others. In the regenerator, thecatalyst is reactivated by reacting the catalyst with the oxidizingagent. In some cases, the deactivated catalyst may comprise residualcarbon and/or coke, which may be removed via reaction with the oxidizingagent in the regenerator. The regenerator in FIG. 1 comprises a ventstream 34 which may include regeneration reaction products, residualoxidizing agent, etc. The vent stream from the regenerator may be passedthrough a catalytic exhaust gas cleanup system to further reduce theconcentrations of CO and hydrocarbons to reduce emissions vented to theatmosphere. Portions of the vent stream 34 may be recycled to the gasfeed 32 of the regenerator 30 to control the heat release of theregeneration process.

The regenerator may be of any suitable size mentioned above inconnection with the reactor or the solids separator. In addition, theregenerator may be operated at elevated temperatures in some cases(e.g., at least about 300° C., 400° C., 500° C., 600° C., 700° C., 800°C., or higher). The residence time of the catalyst in the regeneratormay also be controlled using methods known by those skilled in the art,including those outlined above. In some instances, the mass flow rate ofthe catalyst through the regenerator will be coupled to the flow rate(s)in the reactor and/or solids separator in order to preserve the massbalance, or heat balance, or both heat and mass balance in the system.

As shown in the illustrative embodiment of FIG. 1, the regeneratedcatalyst may exit the regenerator via stream 36. The regeneratedcatalyst may be recycled back to the reactor. In some cases, catalystmay be lost from the system during operation or catalyst may be removedas it deactivates. In some such and other cases, additional “makeup”catalyst may be added to the system from fresh catalyst inventory 4. Asshown illustratively in FIG. 1, the regenerated and makeup catalyst maybe fed to the reactor via a separate stream, or the regenerated andmakeup catalyst may be fed with the fluidization fluid via recyclestream 8, or any selected combination of these.

Referring back to solids separator 40 in FIG. 1, the reaction products(e.g., fluid hydrocarbon products) exit the solids separator via stream44. In some cases, a fraction of stream 44 may be purged. The contentsof the purge stream may be fed to a combustor or a water-gas shiftreactor, for example, to recuperate energy that would otherwise be lostfrom the system. Preferably, the reaction products in stream 44 may befed to condenser 50. The condenser may comprise a heat exchanger whichcondenses at least a portion of the reaction products from a gaseous toa liquid state. The condenser may be used to separate the reactionproducts into gaseous, liquid, and solid fractions. The condenser may bea series of condensers operated at different temperatures and flow ratesrather than a single unit. The operation of condensers is well known tothose skilled in the art. Examples of condensers are described in moredetail in Perry's Chemical Engineers' Handbook, Section 11: “HeatTransfer Equipment.” 8th ed. New York: McGraw-Hill, 2008.

The condenser may also, in some embodiments, make use of pressure changeto condense portions of the product stream. In FIG. 1, stream 52 maycomprise the liquid fraction of the reaction products (e.g., water,aromatic compounds, olefin compounds, etc.), and stream 54 may comprisethe gaseous fraction of the reaction products (e.g., CO, CO₂, H₂,methane, ethylene, propylene, butenes, etc.). In some embodiments, thegaseous fraction may be fed to a vapor recovery system 70. The vaporrecovery system may be used, for example, to recover any selected vaporswithin stream 54 and transport them via stream 72. Stream 72 may becombined with product stream 92 for further purification or as feed tofurther upgrading. In addition, stream 74 may be used to transport CO,CO₂, H₂, methane, and/or other non-recoverable gases from the vaporrecovery system. It should be noted that, in some embodiments, theoptional vapor recovery system may be placed in other locations.

Other products (e.g., excess gas) may be transported to optionalcompressor 100 via stream 76, where they may be compressed and used asfluidization gas in the reactor (stream 102) and/or where they mayassist in transporting the hydrocarbonaceous material to the reactor.

In some embodiments, the liquid fraction is further processed toseparate the water phase from the organic phase in separator 60 inFIG. 1. Aqueous phase 62 obtained from liquids separator 60 may be sentto waste water cleanup or the organic components present in 62 may befurther concentrated in separator 80, for example by membrane separationor distillation or osmotic separation or other methods known to thoseskilled in the art, to obtain a more concentrated stream 84 and a lessconcentrated stream 82. Stream 84 that is more concentrated inhydrocarbonaceous materials may be recycled back to reactor 20 forfurther upgrading to useful and valuable products via catalytic fastpyrolysis.

Organic phase 64 may optionally be fed to a product separator 90.Product separation in 90 can separate the organic materials into a crudeproduct 92 that is enriched in the desired components for transport tofurther purification or processing, and a crude material 94 that isrelatively depleted of useful materials. Stream 94 can be recycled backto reactor 20 for further upgrading via catalytic fast pyrolysis toproduce additional useful products or it can be used as fuel orotherwise disposed of.

As shown in FIG. 1 streams 84 and 94 may be combined or may beseparately fed to reactor 20. Streams 84 and 94 may be combined to beadded to the biomass feed or either 84 or 94 may be separately mixedwith the biomass for introduction into reactor 20.

It should be understood that, while the set of embodiments described byFIG. 1 includes a reactor, solids separator, regenerator, condenser,etc., not all embodiments will involve the use of these elements. Forexample, in some embodiments, the feed stream may be fed to a catalyticfixed bed reactor, reacted, and the reaction products may be collecteddirectly from the reactor and cooled without the use of a dedicatedcondenser. In some instances the product may be fed to a quench tower towhich is fed a cooling fluid, preferably a liquid, along with theproduct stream to cool and condense the products. In some instances,while a dryer, grinding system, solids separator, regenerator,condenser, and/or compressor may be used as part of the process, one ormore of these elements may comprise separate units not fluidicallyand/or integrally connected to the reactor. In other embodiments, one ormore of the dryer, grinding system, solids separator, regenerator,condenser, and/or compressor may be absent. In some embodiments, thedesired reaction product(s) (e.g., liquid aromatic hydrocarbons, olefinhydrocarbons, gaseous products, etc.) may be recovered at any point inthe production process (e.g., after passage through the reactor, afterseparation, after condensation, etc.).

In general, the invention can be any apparatus, process, or integratedsystem having one or any combination of the features discussed in thisspecification.

FIG. 2 presents a flow diagram of the production of a variety ofchemical intermediates labeled as derivatives, polymers, and productsfrom biomass by the process of the instant invention. In FIG. 2 thebiomass feed and processes that conduct biomass to the biomass upgradingplant are designated as 201, processes for preparing the biomass forconversion in the CFP process are shown as 202, and the catalytic fastpyrolysis is indicated as 203. Collection and separation of the fluidhydrocarbons comprises a catalyst separator, 204, catalyst regenerator,205, product separator 206, purification of aromatics 207, gas recyclecompressor, 208, and electrical generator 209. Items 201 through 207,and optionally 208 and 209, comprise the elements of the CFP processthat produces fluid hydrocarbon products. The fluid hydrocarbon products(primary products) are upgraded in a variety of ways, including 1) gasupgrading processes as shown in 201 that include hydroformylation,methanol synthesis, Fischer-Tropsch synthesis, and acetic acidproduction, and 2) aromatics or aromatics and olefin upgrading processesas shown in 211 that optionally utilize additional reactants as otherfeeds 222 and produce chemical intermediates (secondary products) asshown as 221, 231, and 241. Processes that produce the chemicalintermediates are secondary processes, typically conducted in primaryproduct upgrading reactors isolated from the CFP reactor although insome cases the CFP and primary product upgrading reactors could beintegrated. By-products of the secondary upgrading processes can becollected as processing by-products 251 and recycled to the CFP processeither in combination with the stream arising from 201 or 202, or withthe catalyst recycle from 205, or from the gas recycle from compressor208 that feed into the CFP reactor, 203, or some combination of these.

DESCRIPTION OF SOME PREFERRED EMBODIMENTS

Condensation of condensable materials from the pyrolysis products occursby passing them through a condensation train to condense and collect thedesired products as liquid phases. Typically, the condensation trainwill comprise one or more chilled water condensers, one or moreelectrostatic precipitator and one or more coalescence filter, as arewell known in the art, all of which will be connected in series. Whilethe order of the condensers can be varied, it is typical that the firstcondenser is a water cooled condenser with temperatures on the waterside of 15 to 35° C. Additional condensers can be used that are chilledto lower temperatures, for example, from −10 to 15° C. Condensation canalso be effected by quenching the product mixture with a liquid quenchstream, typically water or an organic phase such as a heavy organic, forexample, the less valuable reaction products. All gases that passthrough the condensation train may also be collected at the end of thetrain.

In most embodiments, two liquid phases are condensed from a pyrolysisreactor, an aqueous phase and an organic phase. The aqueous phasecomprises a significant fraction of the condensed phases, for example,the condensed aqueous phase may comprise 20 to 80 mass % of thecondensed phases, in some embodiments, 35 to 65 mass % of the condensedphases. The organic phase may (and typically does) comprise smallamounts of dissolved water as well. The percent water in a liquid phasecan be measured by known methods such as NMR (nuclear magneticresonance), HPLC (high performance liquid chromatography), gaschromatography, or by fractional distillation. Preferably, the mass %water in an organic phase is determined by Karl Fisher titration.

In some embodiments, the aqueous liquid phase is treated such that oneor more organic components are removed, and the resulting liquid, nowenriched in water, is recycled to a pyrolysis reactor. More preferably,water is removed from the aqueous phase and a water-depleted stream isrecycled to the pyrolysis reactor. In some preferred embodiments, theaqueous phase is treated to have at least 10 mass % less water, in someembodiments at least 30% less water, in some embodiments, at least 50%less water, and in some embodiments, 30 to 80% less water. Water can beremoved from the aqueous phase by any suitable method includingdistillation, absorption, filtration, osmosis, membrane separation, orany other process.

In some embodiments the liquid organic phase is separated into a crudefraction enriched in useful products and a second fraction relativelydepleted in useful products. Separations of organic liquids can beaccomplished by distillation, adsorption, membrane separation, osmosisor any other process. The fraction that is relatively depleted in usefulproducts can be optionally recycled to the pyrolysis reactor.

The distillation of either the water or organic phases can beaccomplished by conventional methods using conventional distillationequipment such astray, bubble cap, packed columns or the like.Distillation may be carried out at subatmospheric pressures or atatmospheric pressures. Ordinarily, this distillation will be carried outat subatmospheric pressures with pressures of 1 to 75 kPa beingpreferred. It is, of course, understood that where separations of thecarbonaceous product or the recycle stream are made to narrow therecycle stream by excluding water, the above preferred pressures may besomewhat less preferred. The method of distillation, as well aspressures and other conditions are not to be held limiting to thepresent invention since the choice of such methods to provide thedesired splits in the catalytically pyrolyzed products are well withinthe ability of those skilled in the art. In some cases the heavierproducts will be recycled, in other cases the lighter products will berecycled. With these teachings, one skilled in the art will find littledifficulty in providing the equipment and conditions for obtaining theserecycle fractions by distillation.

Adsorption of the organics dissolved in or suspended in an aqueous phasecan be accomplished by passing the aqueous phase through a bed oforganic materials such as solid biomass, coked catalyst, char, or thelike. The organics in the aqueous phase are preferentially adsorbed onthe bed of organic materials and the water-enriched aqueous phase passesthrough. The organics-enriched biomass or other organics adsorbent canbe fed back to the pyrolysis reactor.

Adsorption of the water dissolved in or suspended in an organic phasecan be accomplished by contacting the organic phase with a bed of wateradsorbent materials or passing the organic phase through a bed of wateradsorbent materials such as silica gel, magnesium sulfate, clays,zeolites or the like at modest temperatures, i.e. less than 200° C., orless than 100° C., or less than 50° C., to remove the water. Theorganic-enriched phase passes through the adsorbent or remains above theadsorbent. The organic phase can be fed back to the pyrolysis reactor.

A filtration process can be used to separate suspended solids from anaqueous or organic phase before, after, or independent of any adsorptionprocess to remove suspended solids or adsorbent materials. Filtrationtechniques are well known to those skilled in the art. Membraneseparation of the organic and aqueous materials in the aqueous ororganic phases can be accomplished by contacting the liquid phase with apermselective membrane in a batch or continuous process. Continuousprocessing according to the invention is achievable wherein an aqueoussolution feed stream containing organic components is passed on one sideand in contact with a hydrophobic, polymeric membrane having selectivityfor the organic components, while a solution sink or vapor vacuum is incontact with the permeate side of the membrane. The lower chemicalpotential of, for example, the organic component solution sink togetherwith counter current relationship of the organic aqueous solution feedstream, provides driving force for permeating organics through theseselective membranes into the organic solution sink. The organic enrichedsolution sink or vapor can be swept or moved by physical means tosuitable processing which promotes the recycling of the organics and anycomplexing solutions. Suitable complexing solutions could be derivedfrom organic fractions of the reaction product including aromatics,phenols, olefins or the like. The membrane permeation step is preferablyoperated under ambient conditions of temperature which can vary over awide range from about −50 to about 250° C. depending upon the selectionof the sweep liquid and the thermal condition of the feed mixture.Higher operating temperatures are frequently desirable because of theincreased rates of permeation; however, lower temperatures may bedesired to reduce energy input.

The permeation membrane is non-porous, that is, free from holes andtears and the like, which destroy the continuity of the membranesurface. Useful membranes are typically organic, polymeric materials.The membranes are preferably in as thin a form as possible which permitssufficient strength and stability for use in the permeation process.Generally separation membranes from about 0.1 to about 15 mils orsomewhat more are utilized. High rates of permeation are obtained withthinner membranes which can be supported with structures such as finemesh wire, screen, porous metals, and ceramic materials. The membranemay be a simple disc or sheet of the membrane substance which issuitably mounted in a duct or pipe, or mounted in a plate and framedfilter press. Other forms of membrane may also be employed such ashollow tubes and fibers through which or around which the feed isapplied or is recirculated with the permeate being removed at the otherside of the tube as a sweep liquid phase. Various other useful shapesand sizes readily adaptable to commercial installations are known tothose skilled in the art. A particularly advantageous method ofseparating and concentrating water soluble organics is to filter theaqueous solution through a layer of biomass so that the organics areabsorbed by the biomass. The organics-impregnated biomass can be furtherdried or otherwise treated and fed to the reactor for CFP upgrading. Inthis way the organics from the water soluble fraction are converted tovaluable products, including aromatics (BTXN), olefins, CO, CO₂, phenoland other valuable materials. After filtering through the biomass, theaqueous solution can be discarded or passed to a water treatmentprocess.

Catalyst components for the CFP process can be selected from anycatalyst known in the art, or as would be understood by those skilled inthe art. Functionally, catalysts may be limited only by the capabilityof any such material to promote and/or effect dehydration,dehydrogenation, isomerization, hydrogen transfer, aromatization,decarbonylation, decarboxylation, aldol condensation and/or any otherreaction or process associated with or related to the pyrolysis of ahydrocarbonaceous material. Catalyst components can be consideredacidic, neutral or basic, as would be understood by those skilled in theart.

The invention is generally applicable to any biomass pyrolysis reaction.Preferably, the biomass feedstock comprises a solid hydrocarbonaceousmaterial. The biomass feed-stock may comprise, for example, any one orcombination of the biomass sources that are mentioned in the Glossarysection. The pyrolysis reactor can be without a solid catalyst; however,preferably, the pyrolysis reactor comprises a solid catalyst forcatalytic fast pyrolysis (CFP). The type of reactor and the type ofsolid catalyst (if present) are not limited, and can be generally of thetype known for conversion of biomass to fluid hydrocarbonaceous streams.Examples of suitable apparatus and process conditions for CFP aredescribed in U.S. Pat. No. 8,277,643 of Huber at al., and in US PatentApplication 20130060070A1 of Huber et al. that are fully incorporatedherein by reference. Conditions for CFP of biomass can be selected fromany one or any combination of the following features (which are notintended to limit the broader aspects of the invention): a zeolitecatalyst, a ZSM-5 catalyst; a zeolite catalyst comprising one or more ofthe following metals: titanium, vanadium, chromium, manganese, iron,cobalt, nickel, copper, zinc, gallium, platinum, palladium, silver,phosphorus, sodium, potassium, magnesium, calcium, tungsten, zirconium,cerium, lanthanum, and combinations thereof; a fluidized bed,circulating bed, or riser reactor; an operating temperature in the rangeof 3000 to 1000° C.; and/or a solid catalyst-to-biomass mass ratio ofbetween 0.1 and 20.

Alkylation

In some embodiments a benzene-rich fraction is separated from thecatalytic fast pyrolysis process and upgraded in a primary productupgrading process comprising the catalytic alkylation of benzene withethylene to produce ethylbenzene or the catalytic alkylation of benzenewith propylene to produce cumene, or some combination of these. Inpracticing some embodiments of this invention, a portion of the effluentof the alkylation reaction zone is reintroduced into the alkylationreaction zone to enhance the yield of useful products viatransalkylation, A polyethylbenzene, such as diethylbenzene,triethylbenzene, and so forth up to even hexaethylbenzene, is apreferred transalkylating agent because each can transalkylate toethylbenzene, regardless of whether each is alkylated by ethylene. Itwould be preferred to not recycle to the alkylation reaction zone astream containing more than 75 wt % ethylbenzene, such as the productstream produced by an ethylbenzene column of the product separationzone.

In embodiments that include the alkylation of benzene by olefins, theratio of the weight of the olefin entering the alkylation catalyst bedin the olefinic feed stream per unit time to the sum of the weights ofcompounds entering the alkylation catalyst bed per the same unit time,multiplied by 100, is generally less than 1.88, preferably less than1.3, and more preferably less than 0.01. This ratio is sometimesreferred to herein as the olefin ratio. The alkylation conditions maycomprise a maximum olefin concentration based on the weight of compoundsentering the alkylation catalyst bed of preferably less than 1.88 wt %,more preferably less than 1.3 wt %, and still more preferably less than0.01 wt %.

The aromatic feed stream and the olefinic feed stream are preferablycombined upstream of the alkylation catalyst bed. The alkylationreaction zone can comprise one or more alkylation catalyst beds and/orone or more alkylation catalyst reactors, and each reactor may containone or more alkylation catalyst beds. A common configuration of analkylation zone employs two alkylation reactors, each of which has twoalkylation catalyst beds. The number of alkylation reactors is typicallyless than eight, and the number of catalyst beds in a given alkylationreactor is typically less than six.

Alkylation conditions for this invention include a molar ratio of phenylgroups per alkyl group of typically from 25:1 to about 1:1. In someembodiments, the molar ratio may be less than 1:1, and may be down to0.75:1 or lower. Preferably, the molar ratio of phenyl groups per ethylgroup (or per propyl group, in cumene production) is below 6:1, and insome embodiments, in the range of 4:1 to 2:1.

In general, for a given molar ratio of alkylation substrate peralkylation agent, especially an olefinic alkylation agent, the greaterthe molar ratio of phenyl groups to alkyl groups in the feed stream, theless is the rise in temperature in the reaction zone that occurs as aresult of the alkylation reactions. Although the reactor may haveindirect heat exchange means to remove the heat as it is produced, thereactor is preferably adiabatic, and so the outlet temperature of theeffluent stream is higher than the inlet temperature of the reactants.The appropriate reaction temperature may be preferably from 100° C. tothe critical temperature of the alkylation substrate, which may be 475°C. or even higher, the inlet temperature in the reaction zone isgenerally from 200 to 260° C., and preferably from 230 to 250° C. Thetemperature rise is typically from 5 to 50° C., and preferably less than20° C. The temperature rise in the reaction zone may be controlled byadjusting the molar ratio of phenyl groups to ethyl groups in the feedstream, for example by recycling portions of the reactor effluent.Recycling reactor effluent to the reaction zone of the alkylationreactor does not interfere in a significant way with the extent of thealkylation or transalkylation reactions, and recycling reactor effluentmay be employed for the purpose of controlling reaction zonetemperatures.

Alkylation is preferably performed in the liquid phase. Consequently,reaction pressure needs to be sufficiently high to ensure at least apartial liquid phase. Where ethylene is the olefin, the pressure rangefor the reactions is usually from about 200 to about 1000 psi(g) (1379to 6985 kPa(g)), more commonly from about 300 to about 600 psi(g) (2069to 4137 kPa(g)), and even more commonly from about 450 to about 600psi(g) (3103 to 4137 kPa(g)). Preferably, the reaction conditions aresufficient to maintain benzene in a liquid phase and are supercriticalconditions for ethylene. For olefins other than ethylene, this inventionmay be practiced generally at a pressure of from 50 to 1000 psi(g) (345to 6985 kPa(g)).

The weight hourly space velocity (WHSV) of ethylene preferably rangesfrom 0.01 to 2.0 hr⁻¹. The WHSV of aromatics, including benzene and apolyalkylaromatic having at least two C₂ ⁺ groups, if any, preferablyranges from 0.3 to 480 hr⁻¹. In a preferred embodiment, in which thepolyalkylaromatic is a diethylbenzene or a triethylbenzene, the molarratio of benzene per ethylene is from 2:1 to 6:1, the WHSV of ethyleneis from 0.1 to 1.0 hr⁻¹, and the WHSV of aromatics, including benzeneand the polyethylbenzenes is from 0.5 to 19 hr⁻¹.

In practicing some embodiments of this invention, the alkylation reactoreffluent stream is separated into at least two portions, in order thatone portion can be recycled and passed to the alkylation reaction zone.In some embodiments a portion of the alkylation effluent is recycled tothe catalytic fast pyrolysis reactor along with, or separate from, anyprimary products of the fast catalytic pyrolysis process.

In some embodiments, when one portion of the alkylation effluent isrecycled to and introduced into an alkylation reaction zone or the CFPreactor, at least one other portion of the alkylation effluent passes toa separation zone for recovering the monoalkyl aromatic. The separationzone may comprise a benzene fractionation column in order to recycleunreacted benzene to the alkylation zone, and an ethylbenzenefractionation column in order to recover ethyl-benzene as product fromthe heavier polyalkylbenzenes. A polyalkylbenzene fractionation columnmay also be used in order to separate diethylbenzenes andtriethylbenzenes from the other higher mass polyalkylbenzenes,particularly where the polyalkylbenzene that is present in the feedstream is a diethylbenzene or a triethylbenzene. The separation zonepreferably does not comprise a deethanizer unless the concentrations ofunreacted ethylene, ethane, or light C₃-paraffins in the reactoreffluent are high enough to justify a step of separating thesecomponents from the alkylation reactor effluent stream.

In addition to producing a fraction comprising the monoalkyl aromatic,the separation zone may also produce one or more other fractions of thealkylation effluent from a portion of the alkylation effluent.Accordingly, as an alternative to, or in addition to recycling a portionof the alkylation effluent to the alkylation reaction zone, some or allof at least one of these other fractions recovered from the separationzone can also passed to the alkylation reaction zone or to the CFPprocess. These other recovered fractions can comprise polyethylbenzenes,which in turn can be recycled to the alkylation reaction zone astransalkylation agents. In some embodiments, several process streamsproduced by the separation zone can be used to supply suchpolyethylbenzenes to the alkylation reaction zone.

The catalyst for the alkylation process may be any alkylation catalystthat is not deactivated rapidly as a consequence of recycling thepolyalkyl aromatic to the alkylation reactor. The catalyst for thealkylation process may comprise one or more aluminosilicate molecularsieves known as zeolites. Zeolite molecular sieves suitable for use inthe present invention are crystalline aluminosilicates which in thecalcined form typically may be represented by the general formula:

Me(n/2O)xSiO₂ yAl₂O₃

where Me is a cation, n is the valence of the cation, x has a value offrom about 5 to 200, and y has a value of from about 2 to 10. The aboveformula is merely a typical representation; however, less common zeoliteformulations, such as those having lower proportions of aluminum or thepresence of additional elements, may also be used. Detailed descriptionsof zeolites may be found in D. W. Breck, Zeolite Molecular Sieves, JohnWiley and Sons, New York 1974, and in other standard references.

The preferred alkylation catalyst for use in the alkylation process is azeolitic catalyst. Suitable zeolites include zeolite beta, Zeolite Y,ZSM-5, PSH-3, MCM-22, MCM-36, MCM-49, and MCM-56. Zeolite beta isdescribed in U.S. Pat. No. 3,308,069 and Re 28,341. The topology ofzeolite beta and the three zeolite beta polytypes are described in thearticle by Higgins, et al., in Zeolites, Vol. 8, November 1988, startingat page 446; and in the letter by M. M. J. Treacy et al., in Nature,Vol. 332, Mar. 17, 1988, starting at page 249. Suitable zeolite betasinclude, but are not limited to, the naturally occurring mixture of thethree polytypes, any one of the three polytypes, or any combination ofthe three polytypes. The use of zeolite beta in alkylation andtransalkylation is disclosed in U.S. Pat. Nos. 4,891,458 and 5,081,323,and the use of pristine zeolite beta in alkylation is disclosed inEuropean Pat. EP 432,814 B1. Suitable zeolite betas include, but are notlimited to, pristine zeolite beta in which the H⁺ ion has at leastpartially replaced the contained metal cation, as disclosed in EuropeanPat. EP 432,814 B1; and zeolite beta into which certain quantities ofalkaline, alkaline-earth, or metallic cations have been introduced byion exchange, as disclosed in U.S. Pat. No. 5,672,799. Variousmodifications of zeolite beta are also suitable for use in thisinvention. Suitable modified zeolite betas include, but are not limitedto, zeolite beta which has been modified by steam treatment and ammoniumion treatment, as disclosed in U.S. Pat. No. 5,522,984; and zeolite betain which the H+ ion has at least partially replaced the contained metalcation, with the zeolite beta being modified by isomorphous substitutionof aluminum by boron, gallium, or iron, as disclosed in European Pat. EP432,814 B1.

It is believed that mordenite zeolite and omega zeolite can also besuitable catalysts for the alkylation process. Suitable zeolites arezeolite beta as disclosed in U.S. Pat. Nos. 4,891,458 and 5,081,323, anda steamed and ammonium exchanged zeolite beta as disclosed in U.S. Pat.No. 5,522, 984. A preferred zeolite beta for use in alkylation processin this invention is disclosed in U.S. Pat. No. 5,723,710. Any of the USpatents mentioned herein are incorporated herein by reference.

The olefin for the reaction can come partly or entirely from thepyrolysis reaction. In this way, it is possible to synthesize styrene inan integrated process using exclusively or primarily (at least 50% bymass, more preferably at least 90% and still more preferably at least95% by mass) biomass-derived materials.

In some embodiments, the alkylation is conducted in the same processstream as the CFP reaction but at a later stage where alkylationcatalyst is present; and in some embodiments, the alkylation isconducted in the same process stream with olefin added in stages alongthe length of the CFP reaction process stream. In some embodiments,alkylation is conducted in a separate reactor, and occurs after thesteps of a CFP reaction and solids removal (such as in a cyclone) andthe catalyst for the CFP reaction and the alkylation reaction can becombined and regenerated together.

An additional advantage to combining the CFP process with an alkylationprocess is that relatively small amounts of olefin can be used (forexample, less than 2%, less than 1% or less than 0.5% by mass of the CFPproduct stream), thus reducing undesired side products, such as1,1-diphenylethane, and the remaining CFP products collected. Theoverall result is upgrading the value of products from the CFP processwithout significantly increasing the amount of undesired by-products. Insome cases, desired alkylated product, such as ethylbenzene is producedwhile fewer undesired by products are produced. Yet another advantagemay be that reacting a product stream from the CFP reaction, such as theproduct stream in an upper portion (for example, above the bottom half)of the fluidized bed reactor, or before any separation, or after partialseparation (such as after removing solids, or after removing solids andseparating an aqueous phase) while result in little or no increase inundesired product since any so-called side products (such as 1,1-DPE)can be captured with an aromatic fraction for use as a fuel or recycledto the CFP reactor. Thus, several potential advantages are created bycombining alkylation with the CFP process in an integrated system.

An integrated process may also involve staged addition of an olefinalong the upward direction of a fluidized bed reactor where one or moretrays of catalyst comprise a mixture of catalyst, with some catalystselected to increase conversion of biomass or biomass-derived components(such as cellulose or cellulose fragments) into smaller molecules andsome catalyst selected to increase the alkylation of aromatics witholefin; thus, in some preferred embodiments, a fluidized bed reactorcomprises a plurality of trays distributed along the length of thereactor (typically oriented perpendicular to gravity) with catalystcomposition varying between one or more trays; in some embodiments witha relatively higher percentage of alkylation catalyst nearer the top ofthe reactor. Although it is recognized that there is often a similaritybetween CFP catalyst and alkylation catalyst, the skilled worker caneasily identify catalysts that are relatively superior for alkylations(for example, this could be done from reading the literature orconducting simple comparative testing).

Styrene

Alkylbenzenes produced by the alkylation of benzene derived from the CFPprocess can be further upgraded to styrene. Examples of these alkylbenzenes are ethylbenzene, cumene (isopropyl benzene), n-propyl benzene,secondary butyl benzene, isobutyl benzene, tertiary butyl benzene,n-butyl benzene, the amyl benzenes, the hexyl benzenes, the heptylbenzenes, the octyl benzenes, and the nonyl benzenes. Higher alkylbenzenes are also obtainable from the alkylation of benzene with thecorresponding olefin. The higher alkylated products also can either bestraight chain or branched chain. In general, the alkylated benzeneshaving more than 4 carbon atoms in their side chains are less desirableas feed stocks since a large proportion of such compounds are convertedto cracked gases which require separation and recovery. Cumene isparticularly desirable as is secondary butyl benzene. The lattercompound produces two useful products, namely, styrene and ethylene. Thecracking is preferably carried out at temperatures in the range of from600 to 850° C. and preferably from 700° to 800° C. Pressure preferablyranges from 0.25 to 10 atmospheres (Absolute pressure, i.e., ata) with0.5 to 5 atmospheres being preferred and 0.5 to 1 being most preferred.

The dehydrogenation of ethylbenzene to styrene in a fluid-bed orfixed-bed reactor/regenerator system, in the presence of a catalystbased on an iron oxide and further promoters, selected, e.g., from metaloxides such as alkaline oxides, earth-alkaline metal oxides and/oroxides of the metals of the group of lanthanides, supported on amodified alumina is envisioned as part of an integrated reactor system.

The dehydrogenation reaction of ethylbenzene to styrene is carried outat temperatures generally ranging from 540 to 630° C. A typical styreneproduction unit comprises several adiabatic reactors in series, withintermediate heating steps at a temperature ranging from 540° C. to 630°C. and with contact times in the order of tenths of a second; a radialflow reactor which operate under vacuum at a pressure ranging from 30.39to 50.65 Kpa (absolute Pascal) (0.3 to 0.5 ata); and water vapor whichis fed with the charge to be dehydrogenated.

Dehydrogenation of ethylbenzene to styrene can also be conducted in anoxidative process in the presence of oxygen containing feed to aid inthe removal of the hydrogen as water or other material and shift theequilibrium towards the production of styrene. The oxygen containingfeed can be oxygen gas, nitrogen oxides, hydrogen peroxide, CO₂, air,sulfur oxide(s), or various oxygenated hydrocarbon compounds (acids,esters, alcohols, ketones).

Thus, the invention can include the synthesis of styrene and,optionally, the use of styrene for the production of polystyrenes (GPPScrystals, high impact HIPS and expandable EPS),acrylonitrile-styrene-butadiene (ABS) and styrene-acrylonitrile (SAN)copolymers and styrene-butadiene rubbers (SBR) is envisioned as part ofthe integrated reactor system.

In some embodiments, the styrene reactor is in thermal contact with thecatalyst regeneration reactor for the CFP process so that some heat fromthe catalyst regeneration is transferred to the process ofdehydrogenating an alkylbenzene. In some embodiments, a hot productstream from the CFP reaction is passed over a dehydrogenation catalyst(preferably iron oxide) and a portion of the alkylbenzenes in the CFPstream are converted to styrene; preferably, ethylbenzene is added tothe stream prior to or during passage over the dehydrogenationcatalyst—this can create a variety of advantages such as cooling theproduct stream (thus reducing the need for heat exchanging condensers),extending catalyst life with no or a reduced need to heat added steam,and increasing the efficiency and decreasing the size of apparatus.

Phenol

Phenol is a basic commodity chemical with many end uses that can beprepared from the cumene derived from products of CFP benzene alkylationwith propylene. Cumene is oxidized in air or with another oxidizingagent to give cumene hydroperoxide, which is subsequently cleaved byacid to provide phenol and acetone. The phenol and acetone are separatedand each one purified to the degree necessary to satisfy its ultimateuse. An integrated process from biomass includes the recycle ofbyproducts of phenol production such as acetone to the CFP processwherein they can be converted to additional aromatics, or olefins, orboth.

Phenol is among the primary products of the CFP process for convertingbiomass to useful chemical intermediates. Separation of phenol from theproduct mixture can be accomplished by a range of techniques includingdistillation, solvent extraction, extractive distillation,crystallization, membrane separation, or other processes well known tothose skilled in the art, or some combination of these.

Phenol can be further upgraded into a self-hardening phenolic resin byreacting phenol and formaldehyde. Phenol derivatives can be made byreaction with a wide range of aldehydes. A hybrid phenolic/polysiloxaneresin can be prepared by reacting phenol with an alkoxy or silanolfunctional siloxane polymer or an aldehyde and further reacting thereaction product thereof with an aldehyde, or with an alkoxy or silanolfunctional siloxane polymer, the sequence depending on the desiredcomposite resin. Phenol resin byproducts can be recycled to the CPFprocess to improve overall process efficiency, except wherein a silanolor other Si-containing material has been introduced, therein producingan integrated reactor process that includes CFP and several subsequentprocesses.

Additional secondary products that can be derived from phenol includealkylphenols, polymethylphenols, ethylphenols, isopropylphenols,sec-butylphenols, tert-butylphenols, tert-pentylphenols,cycloalkylphenols, aralkylphenols, alkenylphenols, indanols, catechol,trihydroxybenzenes, pyrogallol, hydroxyhydroquinone, phloroglucinol,bisphenols (bis-hydroxyarylalkanes, such as bis-phenol A (BPA)),hydroxybiphenyls, and phenol ethers. Other useful secondary productsderived from phenol include diphenylcarbonate, Diphenyl carbonate can beproduced by reacting phenol with carbon monoxide that is also derivedfrom the CFP process, thus producing a fully bio-deriveddiphenylcarbonate. Production of polycarbonates from bio-derivedmaterials can be conducted by the transesterification from BPA anddiphenyl carbonate: The processes that are used to produce secondary andtertiary products from phenol can produce waste streams that can in partbe recycled to the feed of the CFP process for conversion to additionaluseful materials. Polycarbonates that are not suitable for furtherproduction of consumer products can be ground to appropriate sizeparticles and recycled to the CFP process, thus increasing carbonefficiency of the overall process.

Cyclohexane

A benzene-enriched stream obtained from the CFP process can be convertedto cyclohexane by the catalytic hydrogenation of benzene, either throughliquid phase hydrogenation, catalyzed, for example, with Ni Raney at150° C. and about 15 atmosphere pressures (Sabatier, Ind. Eng. Chem. 18,1005 (1925)) or through the process developed by the Institut Francaisdu Petrole wherein benzene and hydrogen-rich gas is fed to aliquid-phase reactor containing Raney nickel catalyst. The nickelsuspension is circulated to improve heat removal, the benzene beingcompletely hydrogenated in a second fixed-bed reactor. Said catalytichydrogenation of benzene can also be carried out by hydrogenation in gasphase, catalyzed with noble metals, mainly platinum supported overalumina, etc., at 200° C. temperatures and about 30 kg/cm² pressures.Benzene production technologies enable the obtention of high puritybenzene, being its purity degree of over 99.99%. Hence, cyclohexane thatis thus obtained by hydrogenation could have similar purity levels.However, hydrogenation reactions take place along with secondaryreactions that produce undesired contaminants especiallymethylcyclopentane (MCP). In an integrated process that converts biomassto chemicals, byproducts such as MCP can be recycled to the CFP reactorfor upgrading to additional aromatics and olefins.

Adipic Acid

Adipic acid is a large volume commodity chemical used for the productionof polymeric compounds. Cyclohexane derived from benzene produced in aCFP process can be used as a precursor for the manufacture of adipicacid. A variety of techniques can be used to convert cyclohexane toadipic acid.

As is well-known, in the oxidation of cyclohexane to adipic acid in thepresence of a cobalt salt, any cobalt salt of an organic acid can beused, see U.S. Pat. No. 3,231,608 to Kollar. Adipic acid is preparedfrom cyclohexane using cobalt as a catalyst, often in the presence ofinitiators (U.S. Pat. No. 4,032,569; U.S. Pat. No. 4,263,453 andJapanese Pat. No. 51075018. U.S. Pat. No. 4,032,569, U.S. Pat. No.5,221,800). Preferably at least about 25 millimols of cobalt be presentper mole of cyclohexane in the process and that temperature be in therange of from about 85° C. to about 105° C., oxygen partial pressure atleast about 150 psia, preferably for a period of about 0.5 to about 3hours. Chromium, manganese, and/or copper may also be used in place or,or in addition to the cobalt catalyst. In some cases. cyclohexane isfirst converted to cyclohexanone and cyclohexanol, and nitric acid canbe used to convert these to adipic acid.

Alternatively, cyclohexane can be converted to adipic acid over a solidheterogeneous catalyst, such as Au, Pd, Pt, Ru and/or Ag on an oxidesupport. See, for example, U.S. Pat. Pub. 2012/0095258.

An alternative process is the reaction of cyclohexane with hydrogenperoxide in a continuous reactor. See, for example, Wen et al, “Acontinuous process for the production of adipic acid via catalyticoxidation of cyclohexane with H₂O₂,” Green Chem. 2012, 2868-2875.

Any of these processes can be integrated with the production ofcyclohexane from pyrolysis of biomass. For example, it is known that theaddition of water to the synthesis can improve the oxidation ofcyclohexane to adipic acid (see U.S. Pat. No. 5,221,800); and in anintegrated process, water resulting from the biomass pyrolysis is addedto the reaction mixture, for example water produced in a biomass dryingstep or water produced from the pyrolysis. The water may be used with orwithout purification. Thus, what is conventionally considered wastewater may be used to improve a synthesis process and reduce waste. Inanother example, “waste” phenol resulting from the biomass pyrolysis canbe hydrogenated and the resulting cyclohexanone and/or cyclohexanolcombined with the cyclohexane to adipic acid process (either in theinitial feed or at an intermediate stage); thus reducing waste andincreasing yield of adipic acid.

Nylon 6,6

Subsequently, nylon-6,6 can be made by the reaction of adipic acid withhexamethylenediamine (HMD). It is also known that polyamides, such asnylon-6,6, can be produced by reaction of diamines and dinitriles in thepresence of water. In an integrated process from biomass to chemicalsundesired byproducts from the synthesis or subsequent reaction ofnylon-6,6, such as monomers and lower polymers, can be recycled to theCFP reactor to produce additional aromatics, thus increasing theefficiency of the overall integrated process.

In some cases, at least a portion of the HMD is made with nitrogenderived from the biomass that is fed to the primary reactor. In somepreferred embodiments, the nylon is made in a downward direction andthere is heat exchange with either the CFP reactor or the system forreactivating catalyst.

Toluene Disproportionation

A toluene-rich fraction separated from the primary product mixture maybe disproportionated to provide a higher value mixture of xylenes andbenzene. The xylene product produced has the equilibrium composition ofapproximately 24 percent of 1,4-(para-xylene), 54 percent of1,3-(meta-xylene), and 22 percent of 1,2-isomer (ortho-xylene). Of thexylene isomers, meta-xylene is normally the least desired product, withortho and para-xylene being the more useful products. Para-xylene is ofparticular value, being useful in the manufacture of terephthalic acidwhich is an intermediate in the manufacture of synthetic fibers such aspolyesters, i.e. polyethylene terephthalate ester (PET). Selectivity top-xylene can be enhanced by selection of an appropriate catalyst such asmodified ZSM-5, see U.S. Pat. No. 6,133,470, and can generally beobtained by treatment of a molecular sieve type catalyst such as azeolite, ALPO or SAPO with an organosilicon modifying agent. Thedisproportionation of a toluene-rich fraction may be carried out attemperatures ranging from about 200° C. to about 600° C. or above and atpressures ranging from atmospheric to perhaps 100 atmospheres or above.The toluene-rich feedstock may be supplied to the reaction zonecontaining the zeolite catalyst at rates providing relatively high spacevelocities. The toluene weight hourly space velocity (WHSV) may begreater than 1. Hydrogen is supplied to the reaction zone at ahydrogen/toluene mole ratio within the range of 3-6. The hydrogenpressure may be 500 psi or more. The toluene feedstock need not berigorously dried before supplying it to the reaction zone and watercontents may exceed 100 ppm.

Enhanced p-Xylene Formation in the CFP Process

The proportion of p-xylene in the CFP process can be increased by usinga p-xylene selective catalyst in an CFP reactor. This may be done eitherin a primary reactor that directly pyrolyzes biomass or in a secondaryreactor that treats at least a portion of the products from the primaryreactor. This catalyst may have dual functionality, catalyzing both theconversion of biomass and enhancing the proportion of p-xylene.

Terephthalic Acid

A para-xylene rich fraction separated from the primary product mixtureor a subsequent product mixture, or some combination of these can beintegrated with a process for producing terephthalic acid (TPA) whereinthe para-xylene rich fraction is oxidized to produce terephthalic acid.The TPA thus produced may also be esterified, e.g., to dimethylterephthalate in the same or separate reactor.

The intermediate product stream containing p-xylene is oxidized toterephthalic acid in a secondary process with a second catalyst. Thereis no need for purification of the intermediate product stream to removeortho-xylene or ethylbenzene. The second catalyst is any catalyst whichcatalyzes oxidation of p-xylene to terephthalic acid, e.g., heavy metalcatalyst such as cobalt and/or manganese, and which optionally mayinclude a catalyst for esterification to dimethyl terephthalate.Advantageously, a costly xylene separation step to be eliminated and theproduct stream of the first contacting can be directly integrated withthe oxidation process to pure terephthalic acid or dimethylterephthalate.

The production of terephthalic acid can be integrated with a CFP processthat produces a para-xylene rich stream or with the para-xyleneseparated from a toluene disproportion process in an integrated system,or both. One process for producing terephthalic acid is the so-calledAmoco process described, e.g., in U.S. Pat. No. 2,833,816. This processinvolves liquid phase air oxidation of p-xylene using multivalent(heavy) metals, particularly cobalt and manganese as catalyst in anacetic acid solvent and with bromine as a renewable source of freeradicals. The terephthalic acid product crystals are recovered, e.g., bycentrifugation, and purified by dissolving the crystals in watercontacting with a hydrogenation catalyst, e.g., noble metal on a carbonsupport, and again recovering the crystals. Dimethyl terephthalate canbe produced by liquid phase esterification of the terephthalic acidusing metal catalysts such as zinc, molybdenum, antimony and tin with alarge excess of methanol.

In another process for producing terephthalic acid, four steps are used,alternating oxidation and esterification to produce dimethylterephthalate, as described, e.g., in British Patent Specification Nos.727,989 and 809,730. First, p-xylene is oxidized with a molecularoxygen-containing gas (air) in a liquid phase in the presence of a heavymetal catalyst such as cobalt, manganese, or mixture of both to producep-toluic acid (PTA) which is esterified with methanol to produce methylp-toluate (MPT). A second oxidation of the MPT with the same catalystand molecular oxygen yields in a liquid phase yields monomethylterephthalate which is esterified to the diester dimethyl terephthalate.

Both terephthalic acid and dimethyl terephthalate are used in theproduction of polyethylene terephthalate (PET) or other polyestersthrough a reaction with glycol, e.g., ethylene glycol or tetramethyleneglycol. Reaction of biomass derived terephthalic acid or dimethylterephthalate with biomass derived glycol can be utilized to produce aPET that is virtually 100% biomass derived.

PET produced from biomass by the inventive process can be further formedinto synthetic fibers; beverage, food and other liquid containers,thermoform plastic materials; and engineering resins in combination withglass or other fiber.

Byproducts of the terephthalic acid production processes, or of thepolymerization processes to produce PET can be recycled to the CFPreactor to produce additional aromatics, olefins, or both olefins andaromatics, thus greatly increasing the carbon efficiency of theintegrated process.

Multistage Reactor

Any of the processes described herein for making intermediates can beconducted in a multistage reactor. Thus, the invention includes anyselected process conducted in a multistage reactor. For example, theprocess can be conducted with the CFP process conducted in the firststage(s) of a multistage, fluidized bed reactor with catalyzeddisproportion of toluene to p-xylene occurring in a later stage. Such aconfiguration can reduce cost, energy, and/or size of the process. Theintegration within a single process stream without product separationmay also increase yield of desired products, for example by utilizingunstable compounds or other intermediates that would not be availableafter a separation step.

EXAMPLES

The following examples demonstrate that by-products of the production ofchemical intermediates can be recycled to a CFP process along withbiomass to produce additional aromatics and olefins. In these examplesfurfural, which has H/C_(eff)=0, is used as a model compound for thereactions of biomass.

Example 1 Furfural

A down-flow fixed bed reactor was fitted with 3.0 g of a commercialspray-dried ZSM-5 catalyst containing 50 wt % ZSM-5 and a silica binder.The reactor was heated to 575° C. under a flow of N₂. A solution ofliquid furfural was fed to the reactor at a rate of 1.23 g/hr (WHSV=0.41hr⁻¹) by means of an HPLC pump. The liquid entered the 0.5 inch diametertubular reactor from the top through a 1/16 inch diameter tube and wascarried along with a flow of N₂ of 97 ml/min. The catalyst bed was heldin place in the reactor tube with a plug of quartz wool below thecatalyst. The product of the reaction was passed into a gas bag.

The flow of furfural was started and continued for 25 minutes, with theproduce gases collected for 5,5-minute time intervals during feed flow,and one 5-minute time interval after the feed flow was stopped and onlyN₂ was flowing. The contents of the 6 gas bags were analyzed by GC witha Shimadzu (GC-2014 model) equipped with TCD and FID detectors, and 40meter Rts-vms capillary column from Restek. The analyses of the 6samples were combined and calculations of the product yields,selectivities, and mass and carbon balances were conducted. Cokedeposited on the catalyst was quantified by using a thermogravimetricanalyzer (TGA) from Shimadzu (TGA-50 model). The data are presented inTable 1.

Example 2 Acetone

The experiment in example 1 was repeated with a fresh charge of catalystand a flow of acetone of 0.81 g/hr (WHSV=0.27 hr⁻¹). The results areincluded in Table 1.

Example 3 Furfural and Acetone Mixture

The experiment in Example 1 was repeated with a fresh charge of catalystand a mixture of furfural and acetone containing 62 weight % furfuraland 38 wt % acetone used as the feed. The flow of the feed mixture was1.2 g/hr (WHSV=0.40 hr⁻¹). The results are included in Table 1.

Example 4 Hexanol and Hexanoic Acid

The experiment in Example 1 was repeated with a fresh charge of catalystand a mixture of 47 weight % hexanol and 53 weight % hexanoic acid usedas the feed. The flow of the feed mixture was 1.23 g/hr (WHSV=0.41hr⁻¹). The results are included in Table 1.

Example 5 Furfural, Hexanol, and Hexanoic Acid

The experiment in Example 1 was repeated with a fresh charge of catalystand a mixture of 47 weight % furfural, 25 weight % hexanol, and 28weight % hexanoic acid as the feed. The flow of the feed mixture was1.29 g/hr (WHSV=0. 43 hr⁻¹). The results are included in Table 1.

TABLE 1 (Experimental results in fixed bed reactor tests) FeedstockHexanol + Hexanol + Hexanoic Furfural + Hexanoic Acid + Furfural AcetoneAcetone Acid Furfural Example 1 2 3 4 5 Temperature (° C.) 575 575 575575 575 H/C_(eff) 0.00 1.33 0.51 1.67 0.90 Conc. (mol C/mol 0.259 0.1760.261 0.287 0.288 N₂) WHSV (h⁻¹) 0.41 0.27 0.40 0.41 0.43 Carbonconversion 100.0 100.0 100.0 100.0 100.0 (%) Yield (% Carbon) Aromatics27.2 40.8 31.8 33.3 29.1 Olefins 9.3 44.7 20.1 37.4 17.7 Methane 0.8 5.12.0 6.3 2.9 CO 34.3 3.5 18.4 5.5 12.8 CO2 3.8 7.9 5.1 0.4 2.0 Coke 30.711.0 23.4 2.8 8.2 Aromatics selectivity (% Carbon) Benzene 43.6 37.741.4 35.8 38.8 Toluene 44.3 46.6 45.3 46.6 45.1 Xylenes 8.5 13.7 11.315.8 13.8 Alkyl Benzenes 0.8 1.1 0.9 1.3 1.2 Styrenes 0.1 0.1 0.1 0.10.1 Indenes 0.5 0.2 0.2 0.1 0.2 Naphthalenes 2.3 0.7 0.8 0.3 0.8 Olefinsselectivity (Carbon %) Ethylene 61.2 56.5 60.7 45.4 51.5 Propylene 34.138.2 34.8 47.5 42.7 Propadiene/propyne 0.6 1.2 0.7 1.6 1.0 C₄ olefins4.1 4.2 3.8 4.7 4.1 C₅ olefins 0.0 0.0 0.0 0.8 0.7 Overall selectivity(Carbon %) Aromatics 25.6 36.1 31.5 38.9 40.1 Olefins 8.7 39.5 20.0 43.724.4 Oxygenates 0.03 0.00 0.02 0.00 0.02 CO 32.3 3.1 18.2 6.4 17.6 CO₂3.6 7.0 5.1 0.4 2.7 Methane 0.7 4.5 2.0 7.3 3.9 Coke 29.0 9.7 23.2 3.311.3 O/C in feed 0.400 0.333 0.375 0.25 0.32 O/C in Olefins + 0.000026 00.000038 0 0.000030 Aromatics H/C in Olefins + 1.31 1.57 1.44 1.57 1.44Aromatics In the Table, H/C_(eff) is calculated as (moles H −2 × molesO)/(moles C)

The results in Table 1 show that by-products of chemical processesproduce additional aromatics and olefins when fed to a CFP process.Furfural is a potential by-product of biomass upgrading by a variety ofbiological processes such as fermentation or thermochemical processessuch as pyrolysis. Example 1 shows that furfural can be converted in aCFP process to useful aromatics and olefins. In Example 2, acetone, aby-product of phenol production, is shown to convert to aromatics andolefins in a CFP process. Example 3 shows that mixtures of acetone thatis a byproduct of further chemical processing of biomass-derived benzeneor other aromatics or olefins, can be converted in a single reactor withbiological molecules such as furfural, that is representative ofbiomass. Acetone recycle from a phenol process boosts the yield ofaromatics above that observed with biomass alone, as represented byfurfural. Example 4 shows that longer chain alcohols and acids such ashexanol and hexanoic acid, that are by-products of adipic acidproduction or other chemical upgrading processes based on CFP aromaticsand olefins, can be recycled and converted to aromatics and olefins in aCFP process. Example 5 shows that a mixture of hexanol and hexanoic acidthat is a byproduct of further chemical processing of biomass-derivedbenzene or other aromatics or olefins, can be converted in a singlereactor with biological molecules such as furfural, that isrepresentative of biomass, and that useful aromatics and olefins areobtained. Hexanol and hexanoic acid recycle from an adipic acid processboosts the yield of aromatics above that observed with biomass alone, asrepresented by furfural.

Each of the Examples 1 through 5 shows that a feedstock that has a highO/C atom ratio can be converted to a product with very low O/C ratio andalmost no oxygen in its product aromatics and olefins. Each of Examples1 through 5 additionally shows that a feedstock with a range ofH/C_(eff) ratios from 0 to 1.67 can be converted to a mixture ofaromatics and olefins with a high H/C_(eff).

Thus, in preferred embodiments, byproducts from the synthesis of one ormore chemical intermediates, which have a H/C_(eff) ratio of from 0 to1.67, in some embodiments from 0 to 1.0, in some embodiments from 0 to0.8, in some embodiments from 0 to 0.5 (these are molar ratios, and inthe case of a product mixture, this is based on the entire mixture) arefed back to a pyrolysis reactor and are converted to a mixture ofaromatics and olefins with a H/C_(eff) of at least 1.0, in someembodiments at least 1.2, and in some embodiments in the ratio of 1.0 or1.2 to 2.2 or 2.0 or 1.5. Preferably, the mixture of aromatics andolefins has an O/C atomic ratio less than 0.01. These characteristicsprovide advantages in process efficiency and higher overall yield ofdesirable chemical intermediates.

What is claimed is:
 1. A method for producing aromatics frombiomass-derived materials comprising: a) feeding a hydrocarbonaceousmaterial comprising fermentation products to a reactor, and pyrolyzingwithin the reactor at least a portion of the hydrocarbonaceous materialto produce one or more pyrolysis products; b) catalytically reacting atleast a portion of the pyrolysis products of step a) to producehydrocarbon products comprising aromatics, and separating at least aportion of the hydrocarbon products comprising aromatics; and c)recovering aromatics from the portion of hydrocarbon products of stepb).
 2. The method of claim 1 wherein the fermentation products comprisefurfural.
 3. A method for producing chemical intermediates comprising:a) feeding a hydrocarbonaceous material to a reactor, and pyrolyzingwithin the reactor at least a portion of the hydrocarbonaceous materialto produce one or more pyrolysis products; b) catalytically reacting atleast a portion of the pyrolysis products of step a) to producehydrocarbon products comprising benzene and/or toluene, and separatingat least a portion of the hydrocarbon products comprising benzene and/ortoluene; c) catalytically reacting at least a portion of biomass-derivedcarbon monoxide to produce methanol; and d) catalytically reacting atleast a portion of the methanol produced in step c) with at least aportion of the benzene and/or toluene produced in step b) to producexylenes.
 4. The method of claim 3 wherein the carbon monoxide of step c)is produced from the pyrolysis of step a).
 5. The method of claim 3wherein the pyrolysis of step a) is catalytic pyrolysis.
 6. A method forproducing one or more fluid chemical intermediates from ahydrocarbonaceous material, comprising: a) feeding a hydrocarbonaceousmaterial to a reactor, and pyrolyzing within the reactor at least aportion of the hydrocarbonaceous material to produce one or morepyrolysis products; b) catalytically reacting at least a portion of thepyrolysis products of step a) to produce hydrocarbon products, andseparating at least a portion of the hydrocarbon products to obtain apredominately benzene containing fraction; and c) alkylating thepredominately benzene containing fraction with ethylene or propylene toproduce an alkylation product.
 7. The method of claim 6 furthercomprising: d) recovering ethylbenzene and/or propylbenzene from thealkylation product of step c).
 8. The method of claim 7 whereinethylbenzene is recovered in step d).
 9. The method of claim 7 furthercomprising: e) dehydrogenating at least a portion of recoveredethylbenzene to produce styrene.
 10. The method of claim 9 furthercomprising: f) recovering styrene produced in step e).
 11. The method ofclaim 10 further comprising: g) polymerizing at least a portion of thestyrene recovered in step f) with at least one component selected fromthe group consisting of butadiene, acrylonitrile, and other olefins, toproduce a polymer.
 12. The method of claim 6 wherein the alkylationproduct of step c) comprises cumene.
 13. The method of claim 12 furthercomprising recovering the cumene of step c).
 14. The method of claim 13further comprising oxidizing at least of portion of the recovered cumeneto produce phenol and acetone.
 15. The method of claim 14 furthercomprising recovering phenol and/or acetone.
 16. A method for producingchemical intermediates comprising: a) feeding a hydrocarbonaceousmaterial to a reactor, and pyrolyzing within the reactor at least aportion of the hydrocarbonaceous material to produce one or morepyrolysis products; b) catalytically reacting at least a portion of thepyrolysis products of step a) to produce hydrocarbon products, andseparating at least a portion of the hydrocarbon products to obtainphenol; c) catalytically hydrogenating at least a portion of the phenolof step b) to cyclohexanone and/or cyclohexanol.
 17. A method forproducing adipic acid comprising: a) feeding a hydrocarbonaceousmaterial to a reactor, and pyrolyzing within the reactor at least aportion of the hydrocarbonaceous material to produce one or morepyrolysis products; b) catalytically reacting at least a portion of thepyrolysis products of step a) to produce hydrocarbon products comprisingpredominantly benzene, and separating at least a portion of thehydrocarbon products comprising predominately benzene into a benzenefraction; c) catalytically hydrogenating at least a portion of thebenzene fraction of step b) to form cyclohexane; and d) oxidizing atleast a portion of the cyclohexane of step c) to produce adipic acid,wherein water utilized in the oxidation of cyclohexane is at least inpart recovered from the pyrolysis reaction of step a) or biomass drying.18. A method for producing polyethyleneterephthalate comprising: a)feeding a hydrocarbonaceous material to a reactor, and pyrolyzing withinthe reactor at least a portion of the hydrocarbonaceous material toproduce one or more pyrolysis products; b) catalytically reacting atleast a portion of the pyrolysis products of step a) to producehydrocarbon products comprising predominantly benzene and/or toluene,and separating at least a portion of the hydrocarbon products comprisingbenzene and/or toluene; c) catalytically reacting at least a portion ofbiomass-derived carbon monoxide to produce methanol; d) catalyticallyreacting at least a portion of the methanol produced in step c) with atleast a portion of the benzene and/or toluene produced in step b) toproduce product comprising xylenes, and recovering p-xylene from theproduct comprising xylenes; e) catalytically oxidizing at least aportion of the p-xylene recovered in step d) to produce terephthalicacid; and f) polymerizing at least a portion of the terephthalic acid ofstep e) with ethylene glycol or ethylene glycol monomethyl ester toproduce polyethyleneterephthalate.
 19. The method of claim 18 whereinthe ethylene glycol or ethylene glycol monomethyl ester of step f) isderived from biomass or is a product of biomass pyrolysis.
 20. Themethod of claim 18 wherein at least a portion of the toluene produced instep b) is disproportionated to produce products comprising p-xylene.21. A method for making a polyethyleneterephthalate bottle by blowmolding, extrusion, stamping, or pressing the polyethyleneterephthalateproduced in step f) of claim
 18. 22. A method for producing chemicalintermediates comprising: a) feeding a hydrocarbonaceous material to areactor, and pyrolyzing within the reactor at least a portion of thehydrocarbonaceous material to produce one or more pyrolysis products; b)catalytically reacting at least a portion of the pyrolysis products ofstep a) to produce hydrocarbon products comprising styrene, andseparating at least a portion of the hydrocarbon products comprisingstyrene; c) polymerizing at least a portion of the styrene of step b)with at least one component selected from the group consisting ofbutadiene, acrylonitrile, and other olefins, to produce a polymer. 23.The method of claim 22 wherein the butadiene, acrylonitrile, or otherolefins are derived from biomass.
 24. A method for producing chemicalintermediates comprising: a) feeding a hydrocarbonaceous material to areactor, and pyrolyzing within the reactor at least a portion of thehydrocarbonaceous material to produce one or more pyrolysis products; b)catalytically reacting at least a portion of the pyrolysis products ofstep a) to produce hydrocarbon products, and separating at least aportion of the hydrocarbon products; c) separating an aqueous phase fromthe pyrolysis products of step a); d) contacting at least a portion ofthe aqueous phase of step c) with biomass to produce a contactedbiomass; and e) feeding the contacted biomass to the reactor of step a).25. The method of claim 24 wherein the contacted biomass of d) is driedbefore it is fed to the reactor of step a).
 26. A method for producingchemical intermediates comprising: a) feeding a hydrocarbonaceousmaterial to a reactor, and pyrolyzing within the reactor at least aportion of the hydrocarbonaceous material to produce one or morepyrolysis products; b) catalytically reacting at least a portion of thepyrolysis products of step a) to produce a hydrocarbon phase and anaqueous phase, and separating at least a portion of the hydrocarbonphase and the aqueous phase; c) concentrating the aqueous phase of stepb), and d) feeding the concentrated aqueous phase to the reactor of stepa).
 27. The method of claim 26 wherein the aqueous phase of step b) isconcentrated in step c) by a method comprising membrane separation,distillation, osmotic separation or combination thereof.